CN104701505A - Negative active material and lithium battery including the material, and method for manufacturing the material - Google Patents

Negative active material and lithium battery including the material, and method for manufacturing the material Download PDF

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Publication number
CN104701505A
CN104701505A CN201410752893.5A CN201410752893A CN104701505A CN 104701505 A CN104701505 A CN 104701505A CN 201410752893 A CN201410752893 A CN 201410752893A CN 104701505 A CN104701505 A CN 104701505A
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China
Prior art keywords
active material
electrode active
negative electrode
metal oxide
crystallization
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Chinese (zh)
Inventor
朴相垠
金载明
朴铉基
韩东熙
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Samsung SDI Co Ltd
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Samsung SDI Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

A negative active material, a negative electrode, a lithium battery including the negative active material, and a method of preparing the negative active material. The negative active material includes a crystalline carbonaceous substrate; and metal oxide nanoparticles disposed on a surface of the crystalline carbonaceous substrate, wherein the metal oxide nanoparticles have a rutile structure. The negative active material may be used to improve high temperature stability and lifespan characteristics of a lithium battery.

Description

Negative electrode active material, comprise its lithium battery and manufacture its method
The cross reference of related application
This application claims priority and the rights and interests of the korean patent application No.10-2013-0153308 that on December 10th, 2013 submits in Korean Intellectual Property Office, its disclosure is by reference to being all incorporated herein.
Technical field
One or more execution mode of the present invention relates to negative electrode active material, comprise the lithium battery of described negative electrode active material and manufacture the method for described negative electrode active material.
Background technology
Have for the high discharge voltage of at least twice of comparable (routine) battery for the portable electron device (such as personal digital assistant (PDA), mobile phone or notebook computer) of information communication, the lithium secondary battery of the middle use such as electric bicycle, electric motor car, and therefore there is high energy density.
Lithium secondary battery by when in Lithium-ion embeding positive pole and negative pole (comprise separately and make to realize the embedding of lithium ion and the active material of deintercalation)/from the oxidation occurred when positive pole and negative pole deintercalation and reduction reaction generation electric energy, wherein organic electrolyte solution or polymer dielectric are between positive pole and negative pole.
Carrying out about various forms ofly can embedding/carbonaceous material (such as synthesis and native graphite or hard carbon) of removal lithium embedded and the research of non-carbonaceous material such as Si.
When the negative material of lithium secondary battery directly contacts electrolyte, described electrolyte can experience reproducibility fracture (cracking) under low electromotive force.Therefore, during the charging process of lithium, the reactivity between the negative material of lithium secondary battery and electrolyte can increase to form film on the surface of negative pole.Here, the reaction temperature in battery is higher, and the reactivity between negative material and electrolyte is larger.Due to described film, lithium ion and electronics are consumed, and make the life characteristic of lithium secondary battery worsen thus.In addition, the exothermal decomposition reactions of described film experience under about 100 DEG C or higher high temperature, and increase along with the amount of described film, the amount increase of heating, this can make the high-temperature stability of element cell worsen.Due to this phenomenon, the high-temperature stability of lithium secondary battery and life characteristic can worsen.
Therefore, exploitation is needed to have the high-temperature stability of improvement and the negative electrode active material of life characteristic.
Summary of the invention
Relate to according to an aspect of one or more execution mode of the present invention and can improve the high-temperature stability of lithium battery and the negative electrode active material of life characteristic.
An aspect according to one or more execution mode of the present invention relates to the negative pole comprising described negative electrode active material.
An aspect according to one or more execution mode of the present invention relates to the lithium battery comprising described negative pole.
An aspect according to one or more execution mode of the present invention relates to the method preparing described negative electrode active material.
Extra aspect will partly be set forth in the description that follows and partly distinct from described description or by provided execution mode practice be learned.
According to one or more execution mode of the present invention, negative electrode active material comprises:
Crystallization carbonaceous substrate (substrate); With
Metal oxide nanoparticles on the surface of described crystallization carbonaceous substrate.
According to one or more execution mode of the present invention, described metal oxide nanoparticles can have rutile structure.
According to one or more execution mode of the present invention, described metal oxide nanoparticles can have and the anatase structured rutile structure mixed.
According to one or more execution mode of the present invention, described metal oxide nanoparticles can comprise at least one metal oxide of the metal being selected from the 2nd race-13 race element.
According to one or more execution mode of the present invention, described metal oxide nanoparticles can comprise the oxide being selected from following at least one metal: zirconium (Zr), nickel (Ni), cobalt (Co), manganese (Mn), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), titanium (Ti), vanadium (V), iron (Fe), copper (Cu), chromium (Cr), zinc (Zn), molybdenum (Mo), niobium (Nb), tantalum (Ta) and aluminium (Al).
According to one or more execution mode of the present invention, described metal oxide nanoparticles can comprise the metal oxide represented by following formula 1.
Formula 1
M aO b
In formula 1,
1≤a≤4,1≤b≤10, and
M can be and is selected from following at least one: titanium (Ti), zirconium (Zr), nickel (Ni), cobalt (Co), manganese (Mn), chromium (Cr), zinc (Zn), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), vanadium (V), iron (Fe), copper (Cu), molybdenum (Mo), niobium (Nb), tantalum (Ta) and aluminium (Al).
According to one or more execution mode of the present invention, described metal oxide nanoparticles can comprise and is selected from following at least one: titanium oxide, aluminium oxide, chromium trioxide, zinc oxide, cupric oxide, magnesium oxide, zirconium dioxide, molybdenum trioxide, vanadic oxide, niobium pentaoxide and tantalum pentoxide.
According to one or more execution mode of the present invention, described metal oxide nanoparticles can comprise the titanium oxide with rutile structure.
According to one or more execution mode of the present invention, described metal oxide nanoparticles can comprise the titanium oxide had with the anatase structured rutile structure mixed.
According to one or more execution mode of the present invention, the average diameter of described metal oxide nanoparticles can be about 1nm-and is about 30nm.
According to one or more execution mode of the present invention, described metal oxide nanoparticles can form the coating layer (as discontinuous layer) with island shape on the surface of described crystallization carbonaceous substrate.
According to one or more execution mode of the present invention, described crystallization carbonaceous substrate can comprise at least one of native graphite, Delanium, expanded graphite (graphite that can expand), Graphene, carbon black and fullerene cigarette ash (soot).
According to one or more execution mode of the present invention, described crystallization carbonaceous substrate can have spherical, flat shape, fiber shape, tube shape or powder shape.
According to one or more execution mode of the present invention, the average diameter of described crystallization carbonaceous substrate can be about 1 μm of-Yue 30 μm.
According to one or more execution mode of the present invention, based on the described crystallization carbonaceous substrate of 100 weight portions, the amount of described metal oxide nanoparticles can be about 0.01 weight portion-Yue 10 weight portion.
According to one or more execution mode of the present invention, negative pole comprises described negative electrode active material.
According to one or more execution mode of the present invention, lithium battery comprises described negative pole.
According to one or more execution mode of the present invention, the method preparing negative electrode active material comprises:
By crystallization carbonaceous substrate, metal oxide precursor and solvent to prepare mixture solution;
By dry for described mixture solution to prepare dry product; With
Product dry described in heat treatment.
According to one or more execution mode of the present invention, described metal oxide precursor can be the slaine comprising and be selected from following at least one metal: titanium (Ti), zirconium (Zr), nickel (Ni), cobalt (Co), manganese (Mn), chromium (Cr), zinc (Zn), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), vanadium (V), iron (Fe), copper (Cu), molybdenum (Mo), niobium (Nb), tantalum (Ta) and aluminium (Al).
According to one or more execution mode of the present invention, the weight ratio of described crystallization carbonaceous substrate to described metal oxide precursor can be about 100:0.01-and is about 100:20.
According to one or more execution mode of the present invention, described heat treatment can be carried out in nitrogen atmosphere or air atmosphere under 700 DEG C or higher temperature.
Accompanying drawing explanation
By the following description of the execution mode considered by reference to the accompanying drawings, these and/or other side will become distinct and be easier to understand, wherein:
Fig. 1 is the schematic diagram of display according to the structure of the negative electrode active material of an execution mode;
Fig. 2 A shows the structure of rutile unit cell and the structure of Fig. 2 B display anatase structure cell;
Fig. 3 is the schematic diagram of display according to the structure of the lithium battery of an execution mode;
Fig. 4 A and 4B is field emission scanning electron microscope (FE-SEM) image of the graphite substrate before and after the heat treatment in manufacture embodiment 1;
Fig. 5 is presented at X-ray diffraction (XRD) analysis result manufacturing embodiment 1 and 2 and manufacture the negative electrode active material used in comparative example 1;
Fig. 6 shows XRD analysis result, and its display is according to the TiO of heat treatment temperature 2crystalline phase;
Fig. 7 is presented at the impedance measurements after the high temperature storage of the coin half-cell battery manufactured in embodiment 2 and comparative example 1;
Fig. 8 is presented at the thermal stability measurement result of the coin half-cell battery manufactured in embodiment 1 and comparative example 1;
Fig. 9 is the figure of the life characteristics at high temperature being presented at the full element cell of coin manufactured in embodiment 3 and 4 and comparative example 2 and 3.
Embodiment
To describe in detail to execution mode now, the example is illustrated in accompanying drawing, and wherein identical Reference numeral refers to identical key element all the time.Here, present embodiment can have different forms and should not be construed as the description being limited to and setting forth herein.Therefore, below by means of only describing described execution mode with reference to the accompanying drawings to explain the aspect of this description."and/or" comprises one or more any and whole combination of associated listed items as used herein, the term.Statement such as " ... at least one (kind) ", when before or after key element list, modifies whole key element list and does not modify the independent key element of described list.In addition, when describing embodiments of the present invention, the use of "available" relates to " one or more execution mode of the present invention ".
Hereinafter, in more detail embodiments of the present invention will be described.
Negative electrode active material according to an embodiment of the invention comprises:
Crystallization carbonaceous substrate; With
Be arranged on the metal oxide nanoparticles on the surface of described crystallization carbonaceous substrate.
Fig. 1 is the schematic diagram of display according to the structure of the negative electrode active material 10 of an execution mode.As shown in fig. 1, negative electrode active material 10 has the metal oxide nanoparticles 12 on the surface being arranged on crystallization carbonaceous substrate 11.
Crystallization carbonaceous substrate 11 comprises crystalline carbon.Here, term " carbonaceous substrate " refers to the carbon comprised at least about 50 % by weight.Such as, described carbonaceous substrate can comprise the carbon at least about 60 % by weight, about 70 % by weight, about 80 % by weight, about 90 % by weight or about 100 % by weight.In addition, term as used in this article " crystallization " refers to the hexagoinal lattice comprised at least about 50 % by weight, and wherein 3 different carbon atoms are covalently bound to and have sp 2the carbon atom of hybridized orbit.Such as, crystallization carbonaceous substrate 11 can comprise the crystalline carbon at least about 60 % by weight, about 70 % by weight, about 80 % by weight, about 90 % by weight or about 100 % by weight.Hexagonal lattice structure can have single layer structure or sandwich construction, or can have the 2 various distressed structures tieing up shapes caused by bending, winding, rotations, partial destruction etc., can the form of Association football be connected with described hexagonal lattice structure.The crystal structure of crystallization carbonaceous substrate 11 is not particularly limited, as long as described structure makes the reversible embedding and the deintercalation that realize lithium ion during charging and discharging process.
According to an execution mode, crystallization carbonaceous substrate 11 can be native graphite, Delanium, expanded graphite, Graphene, carbon black, fullerene cigarette ash or its combination, but crystallization carbonaceous substrate 11 is not limited thereto.
Native graphite is available graphite such as flake graphite, highly crystalline graphite or crystallite (or cryptocrystal) graphite natively.Delanium is the graphite of Prof. Du Yucang, and it is by preparing amorphous carbon at high temperature heat treatment, and the example of Delanium comprises kish, electrographite, secondary graphite and graphite fibre.Expanded graphite refers to the graphite by preparing as follows: chemical substance such as acid or alkali are embedded between the layer of graphite-structure, by its heat treatment, then make the vertical level of molecular structure expand.Graphene refers to mono-layer graphite.Carbon black is the crystalline material of the systematicness had than graphite smaller szie, and when carbon black is heated the long time at the temperature of about 3,000 DEG C, carbon black can be transformed into graphite.Fullerene cigarette ash wherein comprises the carbon compound of the fullerene with the polyhedron bundle (bundle) formed by 60 or more carbon atoms with the amount of about 3 % by weight or more.Crystallization carbonaceous substrate 11 can being combined to form by a kind of crystalline carbonaceous materials or two or more crystalline carbonaceous materials.Such as, can use native graphite and/or Delanium, because during the preparation of negative pole, mixture density can easily increase.
Spherical, flat shape, fiber shape, tube shape and/or powder shape can comprise crystallization carbonaceous substrate 11.Such as, crystallization carbonaceous substrate 11 can have spherical and/or flat shape.Although Fig. 1 shows wherein crystallization carbonaceous substrate 11 have a spherical execution mode, crystallization carbonaceous substrate 11 is not limited thereto.
There is spherical crystallization carbonaceous substrate 11 manufacture by the nodularization (spheronization) of such as crystalline carbon.Such as, the carbonaceous substrate with spherical structure formed by the nodularization of graphite can have the graphite of curved or bending layer structure, or can have and have the curved of squamous shape or squama shape or microstructure that bending graphite flake is formed by multiple.
When crystallization carbonaceous substrate 11 has spherical, the sphericity of crystallization carbonaceous substrate 11 can be about 0.7-about 1.0.Sphericity refers to the value of the deformation extent of the desirable ball of tolerance ball denection, and its value can in the scope of 0-1.0, wherein when described value closer to 1.0 time, described ball is closer to desirable ball.Such as, the sphericity of crystallization carbonaceous substrate 11 can be 0.8-1.0.Such as, the sphericity of crystallization carbonaceous substrate 11 can be 0.9-1.0.On the other hand, the sphericity with the carbonaceous substrate of flat shape can be 0.7 or less.
When being formed as spherical by nodularization process by crystallization carbonaceous substrate 11, crystallization carbonaceous substrate 11 can comprise hole wherein.The porosity of crystallization carbonaceous substrate 11 can be the about 5%-about 30% based on the cumulative volume of crystallization carbonaceous substrate 11, such as, can be about 10%-about 20%.
The average diameter of crystallization carbonaceous substrate 11 is not particularly limited, but when described average diameter is too little, crystallization carbonaceous substrate 11 pairs of electrolyte can be highly reactive, this can make cycle characteristics worsen, with when described average diameter is too large, during the preparation of cathode size, the dispersion stabilization of crystallization carbonaceous substrate 11 can worsen, and the surface of negative pole be can be coarse.Such as, the average diameter of crystallization carbonaceous substrate 11 can be about 1 μm of-Yue 30 μm.At an execution mode, such as, the average diameter of crystallization carbonaceous substrate 11 can be about 5 μm of-Yue 25 μm, or, can be about 10 μm of-Yue 20 μm.
Metal oxide nanoparticles 12 can be arranged on the surface of crystallization carbonaceous substrate 11.
The metal of the metal oxide in metal oxide nanoparticles 12 can be at least one of the element being selected from the 2nd race-13 race in the periodic table of elements.Therefore, in the periodic table of elements element of the 1st race and 14-16 race not included in the metal of described metal oxide.
Such as, the metal of described metal oxide can be at least one metal being selected from titanium (Ti), zirconium (Zr), nickel (Ni), cobalt (Co), manganese (Mn), chromium (Cr), zinc (Zn), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), vanadium (V), iron (Fe), copper (Cu), molybdenum (Mo), niobium (Nb), tantalum (Ta) and aluminium (Al).
Such as, described metal oxide can be represented by following formula 1:
Formula 1
M aO b
In formula 1,1≤a≤4,1≤b≤10, and M is selected from following at least one: Ti, Zr, Ni, Co, Mn, Cr, Zn, B, Mg, Ca, Sr, Ba, V, Fe, Cu, Mo, Nb, Ta and Al.
Such as, described metal oxide can comprise and is selected from following at least one: titanium oxide, aluminium oxide, chromium trioxide, zinc oxide, cupric oxide, magnesium oxide, zirconium dioxide, molybdenum trioxide, vanadic oxide, niobium pentaoxide and tantalum pentoxide.Such as, as described metal oxide, TiO can be used x(1≤x≤2), Al 2o 3, ZrO 2deng.Such as, as described metal oxide, TiO can be used x(1≤x≤2), such as, TiO 2.
The average diameter of metal oxide nanoparticles 12 can be about 1nm-and is about 30nm, about 5nm-and is about 25nm or about 10nm-is about 20nm.
Metal oxide nanoparticles 12 can form coating layer on the surface of crystallization carbonaceous substrate 11.Like this, the coating layer formed by metal oxide nanoparticles 12 can be present in improve the interface stability of crystallization carbonaceous substrate 11 between crystallization carbonaceous substrate 11 and electrolyte, and improves life characteristic and high-temperature stability thus.
TiO x(1≤x≤2), such as, TiO 2, there is high capability retention, low self-discharge rate and low volume-expanding characteristics, and under the charging voltage (0.1V) of graphite, there is low high temperature exothermic characteristic.TiO xat about 1.5V with about have the little but lithium-ion-conducting of abundance between 0V, and therefore, TiO xnot only can serve as the obstacle for hindering the direct contact between electrolyte and crystallization carbonaceous substrate 11, and serve as the path of lithium ion.
Metal oxide nanoparticles 12 pairs of lithiums can be non-activity.Such as, described metal oxide does not react with lithium, makes to form lithium metal oxide.In other words, described metal oxide is not to embed/the negative electrode active material of removal lithium embedded, and is to provide the conductor of the simple transmission passage of lithium ion and/or electronics, and serves as reducing or preventing the protective layer with electrolytical side reaction.Alternatively, metal oxide nanoparticles 12 can be electrical insulator and can be formed and reduces or prevent the protective layer with electrolytical side reaction.
According to an execution mode, metal oxide nanoparticles 12 can have rutile structure.Described rutile structure is formed by the titanium oxide with crystallite form crystal lattice, but described rutile structure is not limited thereto.
Fig. 2 A shows the structure of rutile unit cell, and Fig. 2 B shows the structure of anatase structure cell.The conclusion that the metal oxide nanoparticles with rutile structure can have than having the good high-temperature stability of anatase structured metal oxide nanoparticles can based on following embodiments.
According to an execution mode, metal oxide nanoparticles can have rutile structure and anatase structured combination (mixing) structure.Such as, metal oxide nanoparticles can comprise the titanium oxide with following structure: rutile structure and anatase structured.
The method forming described rutile structure can be any suitable method as known in the art, and is not particularly limited.In order to prepare the metal oxide nanoparticles with rutile structure, such as, the available coated crystallization carbonaceous substrate of coated solution comprising metal oxide precursor, then heat treatment under about 700 DEG C or higher temperature.Rutile structure confirms by X-ray diffraction spectroscopic methodology.
In negative electrode active material, based on the described crystallization carbonaceous substrate of 100 weight portions, the amount of described metal oxide nanoparticles can be about 0.01 weight portion-Yue 10 weight portion.Such as, based on the total weight of described negative electrode active material, the amount of described metal oxide nanoparticles can be about 0.1 % by weight-Yue 5 % by weight or about 0.5 % by weight-Yue 2 % by weight.At an execution mode, when the amount of metal oxide nanoparticles is in above-mentioned scope, the life characteristic of lithium battery improves effectively.
As mentioned above, the wherein said metal oxide nanoparticles described negative electrode active material be arranged on the surface of described crystallization carbonaceous substrate can improve interface stability between described crystallization carbonaceous substrate and described electrolyte to have (improvement) long life-span, high temperature service life and high-temperature stability.
Above-mentioned negative electrode active material is comprised according to the negative pole of another execution mode.
Described negative pole is by such as preparing as follows: will comprise the composition of cathode active materials of negative electrode active material, adhesive and optional conductive agent with setting or predetermined shape, or be coated on collector such as Copper Foil by described composition of cathode active materials.
At an execution mode, preparation comprises the composition of cathode active materials of the mixture of negative electrode active material, conductive agent, adhesive and solvent.Described composition of cathode active materials is directly coated in metal collector to manufacture negative plate.Alternatively, by described composition of cathode active materials curtain coating on independent carrier, then film can be peeled off from described carrier and is then layered in metal collector to manufacture negative plate.The form of described negative pole is not limited to the above form enumerated and can be different from above-mentioned form.
Except above-mentioned negative electrode active material, described composition of cathode active materials can comprise the negative material being used as the negative electrode active material in lithium battery routinely of association area further, such as, described composition of cathode active materials can comprise further and is selected from following at least one: lithium metal, can with the element of lithium alloyage, transition metal oxide, non-transition metal oxides and carbonaceous material.
Such as, described can with the element of lithium alloyage can be silicon (Si), tin (Sn), aluminium (Al), germanium (Ge), plumbous (Pb), bismuth (Bi), antimony (Sb), Si-Y alloy (wherein, Y be alkali metal, alkaline-earth metal, 13-16 race element except Si, transition metal, thulium or its combine) and Sn-Y alloy (wherein Y be alkali metal, alkaline-earth metal, 13-16 race element except Sn, transition metal, thulium or its combine).Element Y can be magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), radium (Ra), scandium (Sc), yttrium (Y), titanium (Ti), zirconium (Zr), hafnium (Hf), (Rf), vanadium (V), niobium (Nb), tantalum (Ta), (Db), chromium (Cr), molybdenum (Mo), tungsten (W), (Sg), technetium (Tc), rhenium (Re), (Bh), iron (Fe), plumbous (Pb), ruthenium (Ru), osmium (Os), (Hs), rhodium (Rh), iridium (Ir), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au), zinc (Zn), cadmium (Cd), boron (B), aluminium (Al), gallium (Ga), tin (Sn), indium (In), germanium (Ge), phosphorus (P), arsenic (As), antimony (Sb), bismuth (Bi), sulphur (S), selenium (Se), tellurium (Te), polonium (Po) or its combination.
Such as, described transition metal oxide can be Li-Ti oxide, barium oxide or lithium-barium oxide.
Such as, described non-transition metal oxides can be SnO 2or SiO x(0<x<2).
The example of described carbonaceous material comprises crystalline carbon, amorphous carbon or its mixture.Described crystalline carbon can be graphite and such as has irregularly shaped, flat shape, chip shape, the native graphite of spherical or fiber shape or synthetic graphite, and described amorphous carbon can be soft carbon (low temperature calcination carbon), hard carbon, mesophase pitch carbonized product, calcined coke or its combination.
Described adhesive can be any suitable adhesive used in the art, such as Kynoar, Vingon, polybenzimidazoles, polyimides, polyvinyl acetate, polyacrylonitrile, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, PVP, polyethylene, polypropylene, polystyrene, polymethyl methacrylate, polyaniline, acrylonitrile butadient styrene, phenolic resins, epoxy resin, PETG, polytetrafluoroethylene, polyphenylene sulfide, polyamidoimide, Polyetherimide, poly-ethylidene sulfone, polyamide, polyacetals, polyphenylene oxide, polybutylene terephthalate (PBT), ethylene-propylene-diene terpolymer (EPDM), the ethylene-propylene-diene terpolymer of sulfonation, butadiene-styrene rubber, fluorubber, or various copolymer, but described adhesive is not limited thereto and can be any suitable adhesive of this area use.Based on the described negative electrode active material of 100 weight portions, the amount of described adhesive can be about 1 weight portion-Yue 50 weight portion.In one embodiment, based on the described negative electrode active material of 100 weight portions, the amount of described adhesive can be about 1 weight portion-Yue 30 weight portion, 1 weight portion-Yue 20 weight portion or about 1 weight portion-Yue 15 weight portion.
Described negative pole optionally comprises conductive agent further to provide conductive channel to described negative electrode active material, to improve conductivity further thus.Described conductive agent can be acetylene black, Ketjen black, native graphite, Delanium, carbon black, carbon fiber etc.; The metal dust of copper, nickel, aluminium or silver or metallic fiber; One or more (polymer) electric conducting materials such as polypheny lene derivatives; Or its mixture.But described conductive agent is not limited thereto, and any suitable conductive agent used in the art can be used.In addition, crystalline carbonaceous materials can be added further as described conductive agent.Suitably can control the amount of described conductive agent.Such as, the verify weight ratio of described conductive agent of described negative electrode active material can be made to add described conductive agent in the amount that about 99:1-is about within the scope of 90:10.
Described solvent can be 1-METHYLPYRROLIDONE (NMP), acetone, water etc., but described solvent is not limited thereto and can be any suitable solvent used in the art.
The amount of described negative electrode active material, conductive agent, adhesive and solvent is for being suitable for the amount of lithium battery.Depend on purposes and the composition of lithium battery, can be omitted described conductive agent, adhesive and solvent one or more.
In addition, described collector can the thickness of about 3 μm of-Yue 500 μm be formed.Described collector is not particularly limited, as long as described collector does not cause chemical change in the battery and has conductivity.The example forming the suitable material of described collector is copper, stainless steel, aluminium, nickel, titanium, calcining carbon, with surface-treated copper and stainless steels such as carbon, nickel, titanium, silver, and the alloy etc. of aluminium and cadmium.In addition, the surface of described collector can be formed uneven microstructure to strengthen the bonding strength to described negative electrode active material.In addition, described collector can use in a variety of forms, and described various ways comprises film, sheet, paper tinsel, net, loose structure, foaming structure, non-woven constructions etc.
The negative pole comprising described negative electrode active material is comprised according to the lithium battery of an execution mode.Described lithium battery can manufacture as follows:
First, negative pole is prepared according to the described method preparing negative pole.
Then, the positive electrode active compound composition of wherein positive active material, conductive agent, adhesive and solvent is prepared.Described positive electrode active compound composition is directly applied with dry to prepare positive plate in metal collector.Alternatively, can by described positive electrode active compound composition curtain coating on independent carrier, then can by the film-stack peeled off from described carrier in metal collector to manufacture positive plate.
Described positive active material can comprise and is selected from following at least one: lithium and cobalt oxides, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, iron lithium phosphate and lithium manganese oxide, but described positive active material is not necessarily limited to this and can be any suitable positive active material used in the art.
Such as, at least one compound represented by following arbitrary formula can be used: Li aa 1-bl bd 2(wherein, 0.90≤a≤1.8 and 0≤b≤0.5); Li ae 1-bl bo 2-cd c(wherein, 0.90≤a≤1.8,0≤b≤0.5, and 0≤c≤0.05); LiE 2-bl bo 4-cd c(wherein, 0≤b≤0.5 and 0≤c≤0.05); Li ani 1-b-cco bl cd α(wherein, 0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05, and 0< α≤2); Li ani 1-b-cco bl co 2-αm α(wherein, 0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05, and 0< α <2); Li ani 1-b-cco bl co 2-αm 2(wherein, 0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05, and 0< α <2); Li ani 1-b-cmn bl cd α(wherein, 0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05, and 0< α≤2); Li ani 1-b-cmn bl co 2-αm α(wherein, 0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05, and 0< α <2); Li ani 1-b-cmn bl co 2-αm 2(wherein, 0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05, and 0< α <2); Li ani be cg do 2(wherein, 0.90≤a≤1.8,0≤b≤0.9,0≤c≤0.5, and 0.001≤d≤0.1); Li ani bco cmn dg eo 2(wherein, 0.90≤a≤1.8,0≤b≤0.9,0≤c≤0.5,0≤d≤0.5, and 0.001≤e≤0.1); Li aniG bo 2(wherein, 0.90≤a≤1.8 and 0.001≤b≤0.1); Li acoG bo 2(wherein, 0.90≤a≤1.8 and 0.001≤b≤0.1); Li amnG bo 2(wherein, 0.90≤a≤1.8 and 0.001≤b≤0.1); Li amn 2g bo 4(wherein, 0.90≤a≤1.8 and 0.001≤b≤0.1); QO 2; QS 2; LiQS 2; V 2o 5; LiV 2o 5; LiRO 2; LiNiVO 4; Li (3-f)j 2(PO 4) 3(0≤f≤2); Li (3-f)fe 2(PO 4) 3(0≤f≤2); And LiFePO 4.
In above formula, A is Ni, Co, Mn or its combination; L is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, thulium or its combination; D is O, F, S, P or its combination; E is Co, Mn or its combination; M is F, S, P or its combination; G is Al, Cr, Mn, Fe, Mg, lanthanum (La), cerium (Ce), Sr, V or its combination; Q is Ti, Mo, Mn or its combination; R is Cr, V, Fe, Sc, Y or its combination; With J be V, Cr, Mn, Co, Ni, Cu or its combination.
Described compound can have coating layer thereon, or can by described compound together with having the compound of coating layer thereon.Described coating layer can comprise following coated element compound: the hydroxyl carbonate of the oxide of coated element, the hydroxide of coated element, the oxyhydroxide of coated element, the carbonic acid oxonium salt of coated element or coated element.The compound forming described coating layer can be unbodied or crystallization.The coated element that described coating layer comprises can be Mg, Al, Co, potassium (K), sodium (Na), calcium (Ca), Si, Ti, V, Sn, Ge, gallium (Ga), B, arsenic (As), Zr or its combination.The method forming described coating layer can be by using described element not cause any suitable method of adverse effect (such as to the character of positive pole in described compound, spraying or dipping), and described method is known to persons of ordinary skill in the art, and therefore, will not repeated it at this and describe.
Such as, LiNiO can be used 2, LiCoO 2, LiMn xo 2x(x=1,2), LiNi 1-xmn xo 2(0<x<1), LiNi 1-x-yco xmn yo 2(0≤x≤0.5,0≤y≤0.5), LiFeO 2, V 2o 5, TiS or MoS.
Conductive agent in described positive electrode active compound composition, adhesive can be identical with those in described composition of cathode active materials with solvent.In addition, plasticizer can be added further to form hole in electrode to described positive electrode active compound composition and/or composition of cathode active materials.
The amount of described positive active material, conductive agent, adhesive and solvent is normally used amount in lithium battery.Depend on purposes and the composition of lithium battery, can be omitted described conductive agent, adhesive and solvent one or more.
Then, the dividing plate be inserted between described positive pole and described negative pole is prepared.Described dividing plate can be any suitable dividing plate for lithium battery.Described dividing plate can have the low resistance to electrolyte ion migration and suitable (such as, excellent) electrolyte solution hold facility.Such as, described dividing plate selectable from glass fiber, polyester, teflon, polyethylene, polypropylene, polytetrafluoroethylene (PTFE) and combination, its can be separately nonwoven or weaving.Such as, the dividing plate that can reel such as polyethylene or polypropylene can be used in lithium ion battery, and the dividing plate with suitable (such as, excellent) electrolyte solution hold facility can be used in lithium ion polymer battery.Such as, described dividing plate is prepared by following method.
By fluoropolymer resin, filler and solvent to prepare baffle combination thing.Described baffle combination thing directly can be applied on electrode also then dry to prepare dividing plate.Alternatively, by also then dry for described baffle combination thing curtain coating on carrier, and the separator membrane peeled off from described carrier can be layered on electrode to prepare dividing plate.
Fluoropolymer resin for the preparation of described dividing plate is not particularly limited and the dividing plate for battery lead plate can be used as to use any suitable material of (utilization).Such as, vinylidene/hexafluoropropylene copolymer, Kynoar (PVDF), polyacrylonitrile, polymethyl methacrylate or its combination can be used.
Then, electrolyte is prepared.
Described electrolyte comprises nonaqueous electrolyte and lithium salts.Described nonaqueous electrolyte can be non-aqueous solution, organic solid electrolyte based or inorganic solid electrolyte.
Described non-aqueous solution can comprise, such as, aprotic organic solvent is METHYLPYRROLIDONE such as, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, gamma-butyrolacton, 1, 2-dimethoxy-ethane, oxolane, 2-methyltetrahydrofuran, methyl-sulfoxide, 1, 3-dioxolanes, 4-methyl-dioxolane, formamide, N, dinethylformamide, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphotriester, trimethoxy-methane, dioxolane derivatives, sulfolane, methyl sulfolane, 1, 3-dimethyl-2-imidazolidinone, polypropylene carbonate ester derivant, tetrahydrofuran derivatives, ether, methyl propionate, or ethyl propionate.
Described organic solid electrolyte based can be, such as, and polythene derivative, polyethylene oxide derivant, poly propylene oxide derivative, phosphate ester polymer, polyester sulfide, polyvinyl alcohol, Kynoar or comprise the polymer of ionic dissociation groups.
Described inorganic solid electrolyte can be, such as, and Li nitride, halide, sulfide or silicate, such as Li 3n, LiI, Li 5nI 2, Li 3n-LiI-LiOH, LiSiO 4, LiSiO 4-LiI-LiOH, Li 2siS 3, Li 4siO 4, Li 4siO 4-LiI-LiOH or Li 3pO 4-Li 2s-SiS 2.
Described lithium salts can be any suitable salt for lithium battery.As the material that can dissolve up hill and dale in nonaqueous electrolyte, such as following at least one can be used: LiCl, LiBr, LiI, LiClO 4, LiBF 4, LiB 10cl 10, LiPF 6, LiCF 3sO 3, LiCF 3cO 2, LiAsF 6, LiSbF 6, LiAlCl 4, CH 3sO 3li, CF 3sO 3li, (CF 3sO 2) 2nLi, chloroboric acid lithium, lower alphatic carboxylic acid lithium, 4-phenylboric acid lithium, imide li etc.
According to used dividing plate and the electrolyte used, lithium battery can be divided into lithium ion battery, lithium ion polymer battery or lithium polymer battery.According to its shape, lithium battery also can be divided into cylinder type lithium battery, rectangular lithium battery, coin-shaped lithium battery or bag shape lithium battery.According to its size, lithium battery also can be divided into large volume (bulk) lithium battery or thin layer lithium battery.Lithium battery also can be primary cell or secondary cell.
The method manufacturing lithium battery is known to persons of ordinary skill in the art, and therefore, will not describe in more detail at this.
Fig. 3 is the schematic diagram of display according to the structure of the lithium battery 30 of an execution mode.
With reference to Fig. 3, lithium battery 30 comprises positive pole 23, negative pole 22 and the dividing plate 24 between positive pole and negative pole 22 and 23.Positive pole 23, negative pole 22 and dividing plate 24 are reeled or folds to be contained in battery case 25.Then, electrolyte is injected battery case 25, use seal member 26 sealed cell shell 25 subsequently, complete the manufacture of lithium battery 30 thus.Battery case 25 can be cylindrical, rectangle or film shell.Lithium battery 30 can be lithium ion battery.
Except existing mobile phone or portable computer, also can be used on according to the lithium battery of an execution mode and such as need the application examples of high power capacity, high-power output and high temperature driven as in electric motor car.In addition, described lithium battery can combine with existing internal combustion engine, fuel cell, ultracapacitor etc. and be used in hybrid electric vehicle etc.Such as, described lithium battery has excellent high magnification ability and life characteristic, and is therefore suitable for electric motor car (EV).Such as, described lithium battery is suitable for plug-in hybrid-power electric vehicle (PHEV).
The method preparing negative electrode active material according to another execution mode comprises:
By crystallization carbonaceous substrate, metal oxide precursor and solvent to prepare mixture solution;
By dry for described mixture solution to prepare dry product; With
Product dry described in heat treatment.
Described metal oxide precursor can be the slaine comprising and be selected from following at least one metal: Ti, Zr, Ni, Co, Mn, Cr, Zn, Mo, Ta, B, Mg, Ca, Sr, Ba, V, Fe, Cu and Al.Described slaine can be hydroxide, oxyhydroxide, alkoxide, sulfate, nitrate and/or carbonate.
Such as, metal alkoxide can be used as metal oxide precursor.Described metal alkoxide can be wherein oxyl (alkoxyl) and is coordinated to the organo-metallic compound of metal ion and can be solation.
Such as, described metal alkoxide can be represented by following formula 2.
Formula 2
M(OR) x
Wherein, 1≤x≤5, R can be C 1-20alkyl, and M is selected from Ti, Zr, Ni, Co, Mn, Cr, Zn, B, Mg, Ca, Sr, Ba, V, Fe, Cu, Mo, Nb, Ta and Al.At least one hydrogen atom in described alkyl can be replaced as follows: halogen atom, the C replaced by halogen atom 1-20alkyl (such as CF 3, CHF 2, CH 2f or CCl 3), C 1-20alkoxyl, C 2-20alkoxyalkyl, hydroxyl, nitro, cyano group, amino, amidino groups, diazanyl, hydrazone group, carboxylic acid or its salt, sulfonyl, sulfamoyl, sulfonic acid or its salt or phosphoric acid or its salt.
The weight ratio of described crystallization carbonaceous substrate to described metal oxide precursor can be about 100:0.01-and is about 100:20, and such as, about 100:0.01-is about 100:10, about 100:0.1-and is about 100:5 or about 100:0.1-is about 100:1.When the amount of described metal alkoxide is too little, coated amount can be little, and therefore, covered effect can be little, and when the amount of described metal alkoxide is too large, the specific capacity of described battery can reduce.
Described solvent can be water, alcohol or its combination, and described alcohol can be C1-C4 lower alcohol, and the example of described C1-C4 lower alcohol is methyl alcohol, ethanol, isopropyl alcohol or its combination.But described solvent is not limited thereto, and any suitable solvent known in the association area that can be used for the target realizing described manufacture method can be utilized.
In above-mentioned manufacture method, can by described crystallization carbonaceous substrate, metal oxide precursor and solvent to prepare mixture solution, can by dry for described mixture solution to obtain dry product, and the product heat treatment of described drying can be formed at negative electrode active material on the surface of described crystallization carbonaceous substrate to obtain wherein metal oxide nanoparticles.
According to an execution mode, described heat treatment can be carried out in nitrogen or air (air) environment under 700 DEG C or higher temperature.Under 700 DEG C or higher heat treatment temperature, can Rutile Type be formed, and lower than at 700 DEG C, only can obtain Anatase.Such as, when described heat treatment temperature be 700 DEG C or higher but lower than 800 DEG C time, the mixture of Anatase and Rutile Type can be obtained, and when described heat treatment temperature is 800 DEG C or higher, the metal oxide nanoparticles that wherein only there is Rutile Type can be formed.According to an execution mode, described heat treatment can carry out about 30 minutes-Yue 10 hours at the temperature of about 700 DEG C of-Yue 900 DEG C.
Described manufacture method can comprise the heat-treated products grinding and obtained by described heat treatment further.
In addition, except above-mentioned wet method, described negative electrode active material is also formed by dry method, and described dry method comprises described metal oxide particle and described crystallization carbonaceous substrate mechanical mixture to form the coating layer comprising described metal oxide nanoparticles on described crystallization carbonaceous substrate.Described mixed method can be mechanical fusion (mechanofusion) method etc.In addition, described dry method can be included in further on described crystallization carbonaceous substrate and form described metal oxide nanoparticles, then by its heat treatment.
Hereinafter, in more detail Example embodiments is described with reference to embodiment.But, described embodiment only for illustrative purposes and not limited field.
Prepare negative electrode active material
manufacture the rutile surrounding phase of embodiment 1:0.5 % by weight
As carbonaceous substrate, 25g had natural graphite powder (product of HitachiChemical) and the 0.44g isopropyl titanate ((Ti (OCH (CH of the average diameter of about 10 μm 3) 2) 4, the product of Aldrich, and production code member: 205273) add 200ml isopropyl alcohol to, then mix to prepare mixture solution.In heatable blender, described mixture solution is stirred simultaneously except desolventizing is to obtain dry powder with 300rpm at the temperature of 100 DEG C.By the powder of described drying at nitrogen (N 2) in atmosphere at the temperature lower calcination 1 hour of 800 DEG C to obtain the product of calcining.The product of described calcining is pulverized the TiO with Rutile Type the surface being prepared in described native graphite to be coated with the amount of 0.5 % by weight 2the negative electrode active material of nano particle.
manufacture the rutile+anatase surrounding phase of embodiment 2:0.5 % by weight
Negative electrode active material is prepared, except calcining heat being changed into except 700 DEG C in the mode identical with manufacture embodiment 1.
manufacture the anatase surrounding phase of comparative example 1:0.5 % by weight
Negative electrode active material is prepared, except calcining heat being changed into except 600 DEG C in the mode identical with manufacture embodiment 1.
manufacture comparative example 2: there is no coated process
Use the average diameter with about 10 μm and not to the native graphite (product of Hitachi Chemical) of any coated process on its surface as negative electrode active material.
evaluation operation example 1: the analysis of coated state
In order to analyze the coated state at the negative electrode active material manufacturing preparation in embodiment 1, field emission scanning electron microscope (FE-SEM) image of native graphite base material before being calcined and is afterwards shown in Fig. 4 A and 4B.
As shown in Figure 4A and 4B, can reach a conclusion, after calcining, TiO 2nano particle is coated on the surface of native graphite as island shape (as discontinuous layer).Be coated with the TiO as island shape 2the graphite cathode active material of nano particle can have the TiO than being coated with complete (or continuous print) layer form 2the lithium ionic mobility that the graphite cathode active material of nano particle is good.
evaluation operation example 2:XRD analyzes
What Fig. 5 display was obtained by use CuK alpha ray is manufacturing embodiment 1 and the XRD analysis result manufacturing the negative electrode active material prepared in comparative example 1.In Figure 5, R represents TiO 2rutile Type and A represents TiO 2anatase.The details of X-ray diffraction pattern analysis condition is as follows:
The model of-instrument: X ' pert PRO MPD (manufacturer: PANalytical)
-maximum rated power: 3kW
-maximum voltage/current: 60kV/60mA
-minimum step: 0.001 °
-2 θ scopes :-40 to+220 °
-diffractometer diameter: 430mm
-measuring condition: sweep speed 1 °/minute, scope 20 to 80 °
As shown in Figure 5, the graphite that heat treated isopropyl titanate is coated at the temperature of 800 DEG C shows the TiO of only Rutile Type 2and the graphite that heat treated isopropyl titanate is coated at the temperature of 700 DEG C has the TiO of the mixed phase of rutile and anatase 2, and heat treated graphite has the TiO of only Anatase at the temperature of 600 DEG C 2.
In addition, in order to confirm TiO 2crystalline phase according to the change of heat treatment temperature, by titanium isopropoxide solution heat treatment at the temperature of 600 DEG C, 700 DEG C, 800 DEG C and 900 DEG C of removing graphite, and to the TiO obtained by it 2nano particle carries out XRD analysis and the result obtained by it is shown in Figure 6.
As shown in Figure 6, the product obtained by the heat treatment at the temperature of 800 DEG C (or higher) only shows Rutile Type and the product obtained by the heat treatment at the temperature of 700 DEG C shows the mixed phase of rutile and anatase, and only shows Anatase by the product of the heat treatment acquisition at the temperature of 600 DEG C.These results are mated with the result obtained by Fig. 5.
Manufacture coin half-cell battery
Following manufacture coin half-cell battery is to analyze according to TiO 2the coated change in high-temperature storage characteristics and thermal stability:
embodiment 1
To the negative electrode active material of preparation in embodiment 1 manufactured and mix with the weight ratio of 90:10 as the polyamidoimide (PAI) of adhesive, then add 1-METHYLPYRROLIDONE with adjusting viscosity with the solid content of 60 % by weight to it, prepare negative electrode active material slurry.
By described negative electrode active material slurry with 9mg/cm 2be coated in there are 10 μm of thickness copper foil current collector on.By the battery lead plate of coating at the temperature of 120 DEG C dry 15 minutes, then suppress to manufacture negative pole.
As to electrode, use Li metal; As dividing plate, use polyethylene separator (product of STAR 20, Asahi); With as electrolyte, use (utilization) be dissolved in ethylene carbonate (EC): ethyl methyl carbonate (EMC): the 1.15M LiPF in the admixture solvent of diethyl carbonate (DEC) (volume ratio of 3:3:4) 6, to manufacture coin half-cell battery.
embodiment 2
Manufacturing coin half-cell battery in the same manner as in example 1, replacing manufacturing except the negative electrode active material of embodiment 1 except using the negative electrode active material manufacturing embodiment 2.
comparative example 1
Manufacturing coin half-cell battery in the same manner as in example 1, replacing manufacturing except the negative electrode active material of embodiment 1 except using the negative electrode active material manufacturing comparative example 2.
evaluation operation example 3: the evaluation of high-temperature storage characteristics
By in embodiment 2 and comparative example 1 manufacture coin half-cell battery with the constant current charge of 0.2C multiplying power until voltage reaches 0.01V (relative to Li), then maintenance 0.01V while under constant voltage completely charging until electric current reaches 0.01C.Then, described coin half-cell battery is stored three days at the temperature of 90 DEG C.Use Solatron device (model name: 1260FRA) to measure and to be about the AC-impedance before storing and afterwards within the scope of 0.1Hz with the alternating current of 0.5mA at about 1000Hz-, and the result obtained by it is shown in Figure 7.
As shown in Figure 7, TiO is coated with 2graphite display than not being coated with TiO 2the increase of the little impedance as high-temperature storage characteristics of graphite.This display is coated with TiO 2graphite have than not being coated with TiO 2graphite improve high-temperature storage characteristics.
evaluation operation example 4: the evaluation of thermal stability
The coin half-cell battery constant current manufactured in embodiment 1 and comparative example 1 is charged until voltage reaches 4.3V (relative to Li) with 0.1CCC/CV.After the voltage reaching 4.3V, described coin half-cell battery is charged until the value of constant current is reduced to 1/10 of original value with 4.3V.After charging, dismantled in the drying chamber by described coin half-cell battery, interference is not occurred between two electrodes, and then the mixture of anticathode carries out sampling and evaluates its thermal stability.The evaluation of thermal stability is carried out by differential scanning calorimetry (DSC) analysis, wherein make the temperature of the mixture of negative pole in the scope of 30 DEG C to 400 DEG C with the interval of 10 DEG C increase with measure according to temperature due to the heat produced by the negative electrode active material in the mixture of negative pole caused by electrolytical reaction, it is converted to mass unit.
Fig. 8 is presented at the DSC result of the coin half-cell battery manufactured in embodiment 1 and comparative example 1.Here, region A is the heating region of membrane degradation process and region B is wherein through temperature (heat release) region that the negative electrode active material of charging decomposes.
As shown in Figure 8, be not coated with TiO 2graphite cathode active material compare, be coated with TiO 2graphite cathode active material demonstrate the less exothermal peak near 300 DEG C.This display, the TiO of lithiumation 2there is the structure of the graphite stable than lithiumation, and therefore, show the less exothermal peak in the B of region.The above results implies, due to TiO 2coated, the thermal stability of negative electrode active material is improved.
Manufacture the full element cell of coin
In order to evaluate life characteristics at high temperature, the full element cell of following manufacture coin:
embodiment 3
Mix at the negative electrode active material manufacturing manufacture in embodiment 1 with the weight ratio of 98:2 with adhesive (wherein butadiene-styrene rubber (SBR) mixes with the weight ratio of 1:1 with carboxymethyl cellulose (CMC)), then add 1-METHYLPYRROLIDONE with adjusting viscosity with the solid content of 60 % by weight to it, prepare negative electrode active material slurry.
By described negative electrode active material slurry with 9mg/cm 2be coated in there are 10 μm of thickness copper foil current collector on.After coating, by the battery lead plate of coating at the temperature of 120 DEG C dry 15 minutes, then suppress to manufacture negative pole.
As positive pole, using the LiCoO as positive active material 2(LCO), as the carbon black of conductor with to mix with the weight ratio of 97.5:1:1.5 as the Kynoar (PVdF) of adhesive and be dispersed in 1-METHYLPYRROLIDONE to prepare anode active material slurry.
By described anode active material slurry with 18mg/cm 2be coated in there are 12 μm of thickness aluminum foil current collector on, then by the battery lead plate of coating at the temperature of 120 DEG C dry 15 minutes, then suppress to manufacture positive pole.
Use the negative pole of the positive pole of above preparation and above preparation, as the polyethylene separator (product of STAR20, Asahi) of dividing plate with as the 1.15M LiPF in the electrolytical admixture solvent being dissolved in EC:EMC:DEC (volume ratio of 3:3:4) 6, to manufacture the full element cell of coin.
embodiment 4
Manufacturing the full element cell of coin in mode in the same manner as in Example 3, replacing manufacturing except the negative electrode active material manufactured in embodiment 1 except being used in the negative electrode active material manufacturing manufacture in embodiment 2.
comparative example 2
Manufacturing the full element cell of coin in mode in the same manner as in Example 3, replacing manufacturing except the negative electrode active material manufactured in embodiment 1 except being used in the negative electrode active material manufacturing manufacture in comparative example 1.
comparative example 3
Manufacturing the full element cell of coin in mode in the same manner as in Example 3, replacing manufacturing except the negative electrode active material manufactured in embodiment 1 except being used in the negative electrode active material manufacturing manufacture in comparative example 2.
evaluation operation example 5: the evaluation of life characteristics at high temperature
In order to evaluate the life characteristics at high temperature of the full element cell of coin manufactured in embodiment 3 and 4 and comparative example 2 and 3, complete for each coin element cell is charged until voltage reaches 0.01V (relative to Li) with 0.2C multiplying power by use constant current at the temperature of 45 DEG C, remain on 0.01V, then with constant-potential charge until reach the electric current of 0.01C.After this, complete for described coin element cell is discharged until reach the voltage of 1.5V (relative to Li) with the constant current of 0.2C.
After this, by complete for described coin element cell with constant current with 0.5C multiplying power charging until reach the voltage of 0.01V (relative to Li), remain on 0.01V, then with constant-potential charge until reach the electric current of 0.01C.After this, complete for described coin element cell is discharged until reach the voltage (formation process) of 1.5V (relative to Li) with the constant current of 0.5C.
By complete for the coin after formation process element cell at the temperature of 60 DEG C with constant current with 1.0C multiplying power charging until reach the voltage of 0.01V (relative to Li), remain on 0.01V, then with constant-potential charge until reach the electric current of 0.01C.After this, complete for coin element cell is discharged until reach the voltage of 1.5V (relative to Li) with the constant current of 1.0C, and 50 times will be cycled to repeat.
The full element cell of coin capability retention at high temperature (CRR) manufactured in embodiment 3 and 4 and comparative example 2 and 3 is shown in Figure 9.CRR is defined by following equation 1.
Equation 1
Capability retention [%]=[discharge capacity in each circulation/first time circulation in discharge capacity] × 100
As shown in Figure 9, TiO is not coated with wherein graphite 2the full element cell of coin (comparative example 3) of nano particle is compared, and comprises the TiO with rutile structure 2the full element cell of coin (embodiment 3) of nano particle and comprise the TiO of wherein rutile structure and anatase structured mixing 2the full element cell of coin (embodiment 4) of nano particle demonstrates better life characteristics at high temperature.But, be not coated with TiO with wherein graphite 2the full element cell of coin (comparative example 3) of nano particle is compared, and comprises and has anatase structured TiO 2the life characteristics at high temperature of the full element cell of coin (comparative example 2) the display deterioration of nano particle.
As mentioned above, one or more according to above execution mode of the present invention, negative electrode active material can be used for the high-temperature stability and the life characteristic that improve lithium battery.
Should be understood that Example embodiments described herein only should be considered and be not used in the object of restriction in the meaning described.Feature in each execution mode or in description should typically be considered to can be used for other similar characteristics in other execution mode or in.

Claims (20)

1. negative electrode active material, comprising:
Crystallization carbonaceous substrate; With
Metal oxide nanoparticles on the surface of described crystallization carbonaceous substrate.
2. the negative electrode active material of claim 1, wherein said metal oxide nanoparticles has rutile structure.
3. the negative electrode active material of claim 1, wherein said metal oxide nanoparticles has and the anatase structured rutile structure mixed.
4. the negative electrode active material of claim 1, wherein said metal oxide nanoparticles comprises at least one metal oxide of the metal being selected from the 2nd race-13 race element.
5. the negative electrode active material of claim 1, wherein said metal oxide nanoparticles comprises the oxide being selected from following at least one metal: zirconium (Zr), nickel (Ni), cobalt (Co), manganese (Mn), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), titanium (Ti), vanadium (V), iron (Fe), copper (Cu), chromium (Cr), zinc (Zn), molybdenum (Mo), niobium (Nb), tantalum (Ta) and aluminium (Al).
6. the negative electrode active material of claim 1, wherein said metal oxide nanoparticles comprises and is selected from following at least one: titanium oxide, aluminium oxide, chromium trioxide, zinc oxide, cupric oxide, magnesium oxide, zirconium dioxide, molybdenum trioxide, vanadic oxide, niobium pentaoxide and tantalum pentoxide.
7. the negative electrode active material of claim 1, wherein said metal oxide nanoparticles comprises the titanium oxide with rutile structure.
8. the negative electrode active material of claim 1, wherein said metal oxide nanoparticles comprises the titanium oxide had with the anatase structured rutile structure mixed.
9. the negative electrode active material of claim 1, the average diameter of wherein said metal oxide nanoparticles is 1nm-30nm.
10. the negative electrode active material of claim 1, wherein said metal oxide nanoparticles forms the coating layer with island shape on the surface of described crystallization carbonaceous substrate.
The negative electrode active material of 11. claims 1, wherein said crystallization carbonaceous substrate comprises at least one of native graphite, Delanium, expanded graphite, Graphene, carbon black and fullerene cigarette ash.
The negative electrode active material of 12. claims 1, wherein said crystallization carbonaceous substrate has spherical, flat shape, fiber shape, tube shape and/or powder shape.
The negative electrode active material of 13. claims 1, the average diameter of wherein said crystallization carbonaceous substrate is 1 μm-30 μm.
The negative electrode active material of 14. claims 1, wherein based on the described crystallization carbonaceous substrate of 100 weight portions, the amount of described metal oxide nanoparticles is 0.01 weight portion-10 weight portion.
15. lithium batteries, it comprises the negative electrode active material according to any one of claim 1-14 at negative pole.
The method of the negative electrode active material of 16. any one of preparation claim 1-14, described method comprises:
By crystallization carbonaceous substrate, metal oxide precursor and solvent to prepare mixture solution;
By dry for described mixture solution to prepare dry product; With
Product dry described in heat treatment.
The method of 17. claims 16, wherein said metal oxide precursor is comprise the slaine being selected from following at least one metal: titanium (Ti), zirconium (Zr), nickel (Ni), cobalt (Co), manganese (Mn), chromium (Cr), zinc (Zn), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), vanadium (V), iron (Fe), copper (Cu), molybdenum (Mo), niobium (Nb), tantalum (Ta) and aluminium (Al).
The method of 18. claims 16, wherein said crystallization carbonaceous substrate is 100:0.01-100:20 to the weight ratio of described metal oxide precursor.
The method of 19. claims 16, wherein said heat treatment is carried out in nitrogen atmosphere or air atmosphere under 700 DEG C or higher temperature.
The method of 20. claims 19, wherein said heat treatment is carried out in described nitrogen atmosphere or described air atmosphere at the temperature of 700 DEG C-900 DEG C.
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